KR20170002914A - Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and, more specifically, to a photosensitive resin composition comprising an alkali-soluble first resin including: repeating units having a specific structure and a repeating unit having a carboxylic acid group in a main chain, thereby being able to effectively realize high sensitivity by relieving oxygen inhibition, to realize high resolution by suppressing the enlargement of the line width of a pattern when applied to products and to improve reactivity and reliability.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same.

In the display field, the photosensitive resin composition is used for forming various photo-curing patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed to form a desired photo-curable pattern. In order to improve the process yield and improve the physical properties of the application target in this process, a photosensitive resin composition having high sensitivity is required .

A method of forming a spacer by a photosensitive resin composition includes coating a photosensitive resin composition on a substrate, irradiating ultraviolet rays through the mask, and forming a spacer at a desired position on the substrate in accordance with a pattern formed on the mask through a developing process.

In the case of forming the spacer in this manner, it is important to increase the cross-link density to improve the mechanical properties, resolution, and top / bottom ratio of the pattern. In order to increase the cross-link density, . Therefore, various studies are under way to improve this.

Korean Patent No. 10-1359470 discloses a photosensitive resin composition comprising an alkali-soluble resin, a photocurable monomer, a photopolymerization initiator, an aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor, and a solvent so as to activate the alkyl radicals generated in the photopolymerization initiator Discloses a technique which further improves photoreactivity and maximizes optical efficiency and has greatly improved sensitivity.

However, there is a need for a photosensitive resin composition having improved sensitivity in which radicals can participate more effectively in a polymerization reaction.

It is an object of the present invention to provide a photosensitive resin composition capable of simultaneously realizing high sensitivity and high resolution.

It is an object of the present invention to provide a photocuring pattern that can be realized in a fine pattern and has excellent adhesion, residual film ratio and mechanical properties.

It is still another object of the present invention to provide an image display device having the photocurable pattern.

1. A photosensitive resin composition comprising an alkali-soluble first resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2) and a repeating unit containing a carboxylic acid group in a main chain:

[Chemical Formula 1]

(2)

(Wherein R ₁ is independently of each other a hydrogen atom or a methyl group and R ₂ is, independently of each other, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 2 to 6 carbon atoms, An aromatic hydrocarbon group having 6 to 14 carbon atoms, and n is an integer of 1 to 9).

2. The photosensitive resin composition according to 1 above, further comprising an alkali-soluble second resin comprising a repeating unit represented by the following formula (3) and a repeating unit containing a carboxylic acid group in the main chain:

(3)

(Wherein R ₃ and R ₄ are, independently of each other, a hydrogen atom or a methyl group).

3. The photosensitive resin composition according to 1 above, wherein the alkali-soluble first resin is contained in an amount of 15 to 60 parts by weight based on 100 parts by weight of the total solid content of the composition.

4. The photosensitive resin composition according to 2 above, wherein the alkali-soluble second resin is contained in an amount of 15 to 50 parts by weight based on 100 parts by weight of the total solid content of the composition.

5. The photosensitive resin composition according to 2 above, wherein the mixing ratio by weight of the alkali-soluble first resin and the alkali-soluble second resin is 1: 0.15 to 2.5.

6. The photosensitive resin composition according to 1 above, further comprising a photopolymerizable compound, a photopolymerization initiator and a solvent.

7. The photosensitive resin composition according to 2 above, further comprising a photopolymerizable compound, a photopolymerization initiator and a solvent.

8. A photocurable pattern produced from the photosensitive resin composition according to any one of items 1 to 7 above.

9. The photopolymerizable composition according to 8 above, wherein the photocurable pattern is selected from the group consisting of an adhesive layer, an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern, and a column spacer pattern. pattern.

10. An image display device comprising the photocuring pattern of the above 9th aspect.

The photosensitive resin composition of the present invention can realize high sensitivity by relaxing oxygen inhibition and at the same time suppressing the enlargement of the line width of the pattern and realizing a high resolution by the fine pattern.

The photosensitive resin composition of the present invention is excellent in developing adhesion, and has excellent residual film ratio and mechanical properties.

Since the photocurable pattern made of the photosensitive resin composition of the present invention can be formed in a fine pattern, high resolution can be realized when applied to a product.

The photosensitive resin composition according to an embodiment of the present invention can exhibit excellent reactivity and storage stability at low temperature curing, and patterns produced therefrom can exhibit high durability such as excellent acid resistance.

1 is a view schematically showing the definition of a T / B ratio.
2 (a) to 2 (e) are SEM photographs of the photocurable patterns formed by the compositions of Examples 1 to 5, respectively.
3 (a) to 3 (c) are SEM photographs of the photocurable patterns formed by the compositions of Comparative Examples 1 to 3, respectively.

The present invention includes an alkali-soluble first resin comprising a repeating unit (a) represented by the following formula (1), a repeating unit (b) represented by the formula (2) and a repeating unit (c) To a photosensitive resin composition capable of realizing high sensitivity effectively by alleviating oxygen inhibition and at the same time suppressing enlargement of a line width of a pattern and realizing a high resolution by a fine pattern when applied to a product and improving reactivity and reliability .

Hereinafter, specific embodiments of the present invention will be described. However, this is merely an example and the present invention is not limited thereto.

<Photosensitive resin composition>

The photosensitive resin composition according to one embodiment of the present invention may include an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive.

In the present invention, when the repeating unit, compound or resin represented by each formula contains an isomer, the repeating unit, compound or isomer represented by the formula, The term &quot; resin &quot; means a representative formula including up to its isomer.

Alkali-soluble resin

A. First Resin

The alkali-soluble first resin according to the present invention is a resin that has reactivity and alkali solubility due to the action of light or heat and can act as a dispersion medium for other components.

In the present invention, "first" of the "first resin" is a term used to distinguish the resin to be described below from other resins that can be added as needed, It is not used.

The alkali-soluble first resin according to the present invention may comprise a repeating unit represented by the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ is a hydrogen atom or a methyl group and R ₂ is, independently of each other, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a cycloalkyl group having 2 to 6 carbon atoms, or an aromatic hydrocarbon having 6 to 14 carbon atoms N is an integer of 1 to 9,

Preferably, R ₂ is independently of each other an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n may be an integer of 1 to 9).

In the coating film coated with the photosensitive resin composition capable of performing the photolithography process, oxygen diffused in the air is present. When the oxygen reacts with the radical generated in the curing process of the photosensitive resin composition, it is stabilized with peroxy radical The radicals are inactivated and the radicals are no longer able to participate in the polymerization reaction, so that the cross-linking density of the entire cured composition is significantly lowered (oxygen inhibition).

In order to solve this problem, it is possible to consider using a tertiary amine additive containing an acidic proton having a very high reactivity to carbon (alpha position) adjacent to the nitrogen atom. In this case, It is impossible to realize a fine pattern by increasing the width (line width) as well as the height of the pattern.

Accordingly, the present invention has an acidic proton having high reactivity to carbon (alpha position) adjacent to a nitrogen atom by including the repeating unit (a) represented by the above formula (1) in an alkali-soluble resin, Can be effectively mitigated and a high sensitivity and high resolution pattern can be obtained.

Further, the alkali-soluble first resin according to the present invention includes a repeating unit represented by the following formula (2)

(2)

(Wherein R ₁ is a hydrogen atom or a methyl group).

Since the alkali-soluble first resin according to the present invention contains the repeating unit (b) represented by the general formula (2) above, the curing degree of the composition can be further improved by increasing the reactivity by heat applied during the curing process, It is possible to improve the reliability.

In addition, the first alkali-soluble resin according to the present invention may contain a repeating unit (c) containing a carboxylic acid group to ensure alkali solubility. The repeating unit containing a carboxylic acid group may be formed using monomers known in the art without particular limitation, and examples thereof include (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (Meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl succinate can be used.

In the present invention, "(meth) acrylic-" refers to "methacryl- "," acrylic- "

In the alkali-soluble first resin, the content of the repeating unit (a), the repeating unit (b) and the repeating unit (c) containing a carboxylic acid group represented by the general formula (1) (A) = 2 to 7 mol%, (b) to 50 mol%, and (c) = 5 to 40 mol% ) = 60 to 85 mol%, and (c) = 10 to 35 mol%.

The first resin according to the present invention may be formed only of the repeating units represented by the formulas (1) and (2) and the carboxylic acid group. In addition to the repeating units represented by the formulas (1) and (2) and the carboxylic acid group, other monomers (D) may be further included.

The structure for forming the repeating unit that can be added to the first resin is not particularly limited, and examples thereof include styrene, vinyltoluene, vinylnaphthalene, N-benzylmaleimide, benzyl (meth) acrylate, phenoxyethylene glycol (Meth) acrylate, phenoxyethyleneglycol (meth) acrylate, (2-phenyl) phenoxyethoxy (meth) acrylate, 2-hydroxy- (Meth) acrylate, methoxyethyleneglycol (meth) acrylate, methoxyethyleneglycol (meth) acrylate, methoxyethyleneglycol A structure derived from a monomer selected from the group consisting of methoxy ethylene glycol (meth) acrylate, methoxy ethylene glycol (meth) acrylate and methoxy tetraethylene glycol (meth) acrylate. These may be used alone or in combination of two or more.

In addition to the repeating units represented by formulas (1) and (2) and the carboxylic acid group, in addition to the repeating units (d) formed from other monomers known in the art, the content of each repeating unit is preferably (A) = 2 to 10 mol%, (b) = 50 to 92 mol%, (c) = 3 to 40 mol%, and (d) = 2 to 40 mol% ) = 3 to 8 mol%, (b) = 55 to 86 mol%, (c) = 6 to 35 mol%, and (d) = 5 to 35 mol%.

The alkali-soluble first resin according to the present invention preferably has a weight average molecular weight of 10,000 to 30,000. It is possible to exhibit the most excellent pattern forming property and chemical resistance in the above molecular weight range.

The content of the alkali-soluble first resin according to the present invention is not particularly limited and may be, for example, 15 to 60 parts by weight based on 100 parts by weight of the total solid content of the composition. When included in the above range, the alkali-soluble resin improves the mechanical reliability after the final curing and can realize an excellent shape at the time of pattern formation in the photolithography process.

B. Second Resin

If necessary, the photosensitive resin composition according to one embodiment of the present invention may contain, as an alkali-soluble resin, a resin containing a repeating unit (e) represented by the following formula (3) and a repeating unit 2 resin: &lt; RTI ID = 0.0 &gt;

(3)

(Wherein R ₃ and R ₄ are, independently of each other, a hydrogen atom or a methyl group).

Since the photosensitive resin composition according to the present invention contains the alkali-soluble second resin containing the repeating unit (e) represented by the above-mentioned formula (3), the crosslinking density of the photosensitive resin composition can be increased and the residual film ratio and mechanical properties Etc. can be improved.

In addition, the alkali-soluble second resin may contain a repeating unit (f) containing a carboxylic acid group, and the repeating unit containing the carboxylic acid group described in the first resin may be used in the same range.

The second alkali-soluble resin according to the present invention may be formed by further containing other comonomers capable of copolymerization, if necessary.

Examples of such comonomers include styrene, vinyltoluene, vinylnaphthalene, N-benzylmaleimide, benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) Phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropoxy (meth) acrylate, 2- Acrylate, methoxyethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy diethylene glycol (Meth) acrylate, which may be used singly or in combination of two or more thereof (recurring unit g).

The comonomer may further comprise a monomer represented by the following formula (4) (recurring unit h):

[Chemical Formula 4]

(Wherein n is 0 or 1, and R ₅ and R ₆ are each independently hydrogen, an aliphatic or aromatic hydrocarbon having 1 to 12 carbon atoms and / or a heteroatom, and R ₇ and R ₈ , R ₉ and R ₁₀ are independently selected from the group consisting of hydrogen, an aliphatic or aromatic hydrocarbon having 1 to 30 carbon atoms and / or a hetero atom, and two of R ₇ , R ₈ , R ₉ and R ₁₀ are selected and connected In the form of rings or unconnected branches).

The heteroatom may exist on the main skeleton or branch, and may exist in the form of a carbonyl group, an ether group, an alcohol group, an amine group, a heterocycle, and the like.

For example, the formula (4) may be selected from the group consisting of the following formula (recurring unit h).

The second resin according to the present invention may be formed only of the repeating units represented by the repeating units (e), (f), (g) and (h) ) And (h) as well as other monomers known in the art.

(E) = 10 to 20, the content of each of the repeating units in the second resin may be, for example, (E) = 15 to 25 mol%, (f) = 5 to 25 mol%, (g) = 50 to 70 mol% (f) = 10 to 20 mol%, (g) = 55 to 65 mol%, and (h) = 3 to 7 mol%.

The second alkali-soluble resin according to the present invention preferably has a weight average molecular weight of 5,000 to 20,000. It is possible to exhibit the most excellent crosslinking property in the molecular weight range.

The content of the alkali-soluble second resin according to the present invention is not particularly limited, but may be, for example, 15 to 50 parts by weight based on 100 parts by weight of the solid content of the composition. When included in the above range, the alkali-soluble resin is advantageous in controlling the pattern line width in the lithography process, and can improve the adhesion to the lower substrate and the property that helps secure the margin in the developing process even when a large amount of the hydrophobic component is added .

The weight ratio of the first resin to the second resin may be 1: 0.15 to 2.5, preferably 1: 0.30 to 1.5, according to an embodiment of the present invention. If the content of the second resin exceeds 3 times the weight of the first resin, the mechanical reliability or chemical resistance after the thermosetting step may be deteriorated. If the content of the second resin exceeds 5 times the weight of the first resin, The adhesion in the developing step is lowered, and the formed pattern may be broken.

In the present invention, the respective repeating units represented by the first and second resins should not be construed as being limited as shown, and the sub-repeating units in the parentheses can freely be located at any position of the chain within a predetermined mole percent range. In other words, although the parentheses of each repeating unit are represented by one block in order to express the mol%, each sub-repeating unit can be placed in blocks or separately as long as it is within the resin.

The acid value of the alkali-soluble resin according to the present invention is preferably in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, excellent developability and long-term stability can be obtained.

The total content of the alkali-soluble resin is not particularly limited and may be, for example, 10 to 90 parts by weight, preferably 25 to 80 parts by weight, based on 100 parts by weight of the total solid content of the composition. When it is contained within the above-mentioned range, the alkali-soluble resin can be formed into a photo-curable pattern having good solubility in developer and excellent developing property, good adhesion to the lower substrate and excellent mechanical properties.

Photopolymerization  compound

The photopolymerizable compound used in the photosensitive resin composition of the present invention increases the crosslinking density during the manufacturing process and can enhance the mechanical properties of the photocuring pattern.

The photopolymerizable compound can be used without any particular limitation in the art, and examples thereof include monofunctional monomers, bifunctional monomers and other multifunctional monomers. The type of the photopolymerizable monomer is not particularly limited, and examples thereof include the following compounds have.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexa (metha) Propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

The content of the photopolymerizable compound is not particularly limited and may be, for example, 10 to 90 parts by weight, preferably 30 to 80 parts by weight based on 100 parts by weight of the alkali-soluble resin based on the solid content in the photosensitive resin composition do. When the polymerizable compound is contained in the above-mentioned content range, it can have excellent durability and can improve the developability of the composition.

Light curing Initiator

The photopolymerization initiator according to the present invention is not particularly limited as long as it can polymerize the photopolymerizable compound, and examples thereof include acetophenone compounds, benzophenone compounds, triazine compounds, At least one compound selected from the group consisting of an azo compound, a thioxanthone compound, an oxime ester compound and an aminophenyl ketone compound can be used, and it is preferable to use an oxime ester compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted by a carboalkoxy group , Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl- Bis (o-methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, a bis The type compound and the like can be given:

[Chemical Formula 5]

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone And the like.

Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octanedione, (O-benzoyloxime), ethanone-1- (9-ethyl) -6- Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeca), NCI-831 (Adeka), CGI-124 ), And the like, and preferably an oxime ester compound represented by the following formula (6):

[Chemical Formula 6]

Specific examples of the aminophenyl ketone-based compound include 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, methyl 4- (dimethylamino) benzoate, ethyl 4- (dimethylamino) benzoate, methyl 4- Ethylamino) benzoate, ethyl 4- (diethylamino) benzoate, 2-butoxyethyl 4- (dimethylamino) benzoate, isoamyl 4- (dimethylamino) benzoate, (Dimethylamino) benzoate, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4,4'bis (dimethylamino) benzophenone, 4,4'bis (diethylamino) benzophenone, Preferably an aminophenyl ketone-based compound represented by the following formula (7): &lt; EMI ID =

(7)

The photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition according to the present invention contains a photopolymerization initiator, the sensitivity can be further increased and the productivity can be improved.

Examples of the photopolymerization initiator include at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (Diethylamino) benzophenone, and the like, and it is preferable to use an aromatic amine compound.

Concrete examples of the carboxylic acid compound include aromatic heteroacetic acid compounds. Phenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like can be used. .

The content of the photopolymerization initiator is not particularly limited and may be, for example, 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the photosensitive resin composition based on the solid content. When the above range is satisfied, the sensitivity of the photosensitive resin composition is increased and the exposure time is shortened, so that productivity is improved, high resolution can be maintained, and the strength of the formed pixel portion and smoothness on the surface of the pixel portion can be improved .

menstruum

The solvent may be any solvent as long as it is commonly used in the art.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and ethylene glycol monoethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate; Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxypropylacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butyl Methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, , Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid ethyl, 3-propoxypropionate, Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as? -butyrolactone. The solvents exemplified herein may be used alone or in combination of two or more.

The solvent may be selected from esters such as alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate And more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl and the like can be used.

The solvent content may be included in the photosensitive resin composition in an amount of 40 to 95 parts by weight, preferably 45 to 85 parts by weight based on 100 parts by weight of the total amount. When the above-mentioned range is satisfied, it is preferable because the coating property is improved when applied by a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater), an ink jet or the like.

additive

The photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, chain transfer agents and the like.

Specific examples of the filler include glass, silica and alumina.

Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and their brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

As the leveling agent, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. Two or more species may be used in combination.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Asahi Glass Co., Ltd.), SORPARS (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), FERRAD (manufactured by Sumitomo 3M Ltd.) , And PB821 (manufactured by Ajinomoto Co., Ltd.).

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- Bis [2- {3- [3- tert -butyl] benzo [d, f] [1,3,2] dioxaphospepine, 3,9- -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like, (6-tert-butyl-3-methylphenol).

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like.

< Photocuring  Pattern and image display device>

An object of the present invention is to provide an image display device including the photo-curable pattern made of the photosensitive resin composition and the photo-curable pattern.

The photocurable pattern prepared from the photosensitive resin composition is capable of CD-Bias control and has excellent T / B ratio, developability, adhesion, and mechanical properties. As a result, it can be used in various patterns such as an adhesive layer, an array flattening film, a protective film, an insulating film pattern, etc. in an image display apparatus, and can be used as a photoresist, a black matrix, a column spacer pattern, And is particularly well suited as a spacer pattern.

The image display device having the light curing pattern or using the pattern during the manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like. However, the present invention is not limited thereto, and all image display devices Can be exemplified.

The method for producing the photocurable pattern according to the present invention is not particularly limited and may be a known method in the art. For example, the photosensitive resin composition of the present invention may be applied on a substrate, Followed by a development step) to form a photo-curable pattern.

First, a photosensitive resin composition is coated on a substrate and then heated and dried to remove a volatile component such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coat method or a slit coat method. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is 70 to 100 DEG C which is a relatively low temperature. The thickness of the coating film after drying by heating is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

As the ultraviolet ray, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) or the like can be used. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. If desired, the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, and a desired pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, the substrate is washed with water and subjected to post-baking at a relatively low temperature of 100 to 150 DEG C for 10 to 60 minutes.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to be illustrative of the present invention and are not intended to limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made in the manufacturing examples and the embodiments within the scope of the claims, and such variations and modifications are within the scope of the appended claims.

Manufacturing example  1. Synthesis of alkali-soluble resin (first resin (A-1))

[A-1]

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. 154.2 g (0.70 mol) of a mixture of the following formulas (8) and (9) (molar ratio 50:50), 17.7 g (0.15 mol) of vinyltoluene, 7.9 g (0.05 mol) of dimethylaminoethyl methacrylate, and 8.6 g (0.10 mol) was dissolved in 150 g of diethylene glycol methyl ethyl ether to prepare a solution:

[Chemical Formula 8]

[Chemical Formula 9]

The prepared solution was dropped into a flask using a dropping funnel, 27.9 g (0.11 mol) of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved in diethylene glycol methyl ethyl ether 200 g was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (Resin A-3) having a solid content of 40.6% by weight and an acid value of 118 mg- 1) was obtained.

The resin A-1 thus obtained had a weight average molecular weight Mw of 6,500 and a molecular weight distribution of 1.88.

Manufacturing example  2. Synthesis of alkali-soluble resin (first resin (A-2))

[A-2]

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After raising the temperature to 100 캜, 24.5 g Azobis (2,4-dimethylvalerosulfonate) was added to a mixture containing 4.7 g (0.05 mole) of norbornene, 72.1 g (0.61 mole) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate Nitrile) was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 ° C for 5 hours.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 28.4 g (0.20 mol) of glycidyl methacrylate (59 mol% based on the acrylic acid used in the present reaction) was charged into the flask, and the reaction was continued at 110 DEG C for 6 hours To obtain an unsaturated group-containing resin A-2 having a solid acid value of 70 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 14,500 and the molecular weight distribution (Mw / Mn) was 2.1.

Manufacturing example  3. Synthesis of alkali-soluble resin (second resin (A-3))

[A-3]

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. 187.2 g (0.85 mol) of the mixture of the above formulas 8 and 9 (molar ratio 50:50), 7.9 g (0.05 mol) of dimethylaminoethyl methacrylate and 8.6 g (0.10 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol And dissolved in 150 g of methyl ethyl ether to prepare a solution.

The prepared solution was dropped into a flask using a dropping funnel, 27.9 g (0.11 mol) of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved in diethylene glycol methyl ethyl ether 200 g was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (resin A-2) having a solid content of 41.2% by mass and an acid value of 86 mg- 3) was obtained.

The resin A-3 thus obtained had a weight average molecular weight Mw of 6,800 and a molecular weight distribution of 1.85.

Manufacturing example  4. Synthesis of alkali-soluble resin (A-4)

[A-4]

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. Next, 210.2 g (0.95 mol) of a mixture of the above formulas 8 and 9 (molar ratio 50:50) and 14.5 g (0.17 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ethyl ether to prepare a solution .

The prepared solution was dropped into a flask using a dropping funnel, 27.9 g (0.11 mol) of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved in diethylene glycol methyl ethyl ether 200 g was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (Resin A-2) having a solids content of 41.6% by weight and an acid value of 65 mg-KOH / 4) was obtained.

The resin A-4 thus obtained had a weight average molecular weight Mw of 8,300 and a molecular weight distribution of 1.81.

Manufacturing example  5. Synthesis of alkali-soluble resin (A-5)

[A-5]

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. 154.2 g (0.70 mol) of the mixture of the above formulas 8 and 9 (molar ratio 50:50), 23.6 g (0.20 mol) of vinyltoluene and 8.6 g (0.10 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ethyl ether 150 g to prepare a solution.

The prepared solution was dropped into a flask using a dropping funnel, 27.9 g (0.11 mol) of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved in diethylene glycol methyl ethyl ether 200 g was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a copolymer (Resin A-1) having a solid content of 42.0% by mass and an acid value of 78 mg- 5) was obtained.

The resin A-5 thus obtained had a weight average molecular weight Mw of 7,200 and a molecular weight distribution of 1.87.

Example  And Comparative Example

A photosensitive resin composition having the composition and the content (parts by weight) shown in Table 1 below was prepared.

division Example Comparative Example One 2 3 4 5 One 2 3 The alkali-soluble resin (A) A-1 25.0 25.0 25.0 - 50.0 - - - A-2 25.0 25.0 25.0 25.0 - 50.0 25.0 25.0 A-3 - - - 25.0 - - - - A-4 - - - - - - 25.0 - A-5 - - - - - - - 25.0 The photopolymerizable compound (B) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 The photopolymerization initiator (C) C-1 2.0 - - - - - - - C-2 - 2.0 - - - - - - C-3 - - 2.0 2.0 2.0 2.0 2.0 2.0 C-4 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 C-5 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Additive (E) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Solvent (S) S-1 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 S-2 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0

A-1: An alkali-soluble resin represented by the formula (A-1)

A-2: An alkali-soluble resin represented by the formula (A-2)

A-3: An alkali-soluble resin represented by the formula (A-3)

A-4: An alkali-soluble resin represented by the formula (A-4)

A-5: An alkali-soluble resin represented by the formula (A-5)

B: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Yakuza Co., Ltd.)

C-1: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM manufactured by Hodogaya Chemical Co.,

C-2: 2,2'-bis (o-methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (HABI-

C-3: A non-imidazole-based compound represented by the general formula (5)

C-4: An oxime ester compound represented by the formula (6)

C-5: Aminophenyl ketone compound represented by the general formula (7)

E: 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (BBM-S manufactured by Sumitomo Fine Chemical)

S-1: Diethylene glycol methyl ethyl ether

S-2: Propylene glycol monomethyl ether acetate

Test Methods

A glass substrate (Eagle 2000; Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on the glass substrate, and then pre-baked at 90 DEG C for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature, the substrate was exposed to light at an exposure dose of 60 mJ / cm 2 (based on 365 nm) using an exposure apparatus (UX-1100SM; Ushio Co., Ltd.) with an interval of 200 μm from the quartz glass photomask Respectively. At this time, the photomask used was a photomask in which the following pattern was formed on the same plane.

The coating film was exposed to an aqueous developer containing circular openings (patterns) each having a diameter of 10 탆 and a distance of 100 탆 and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation at 25 캜 for 60 seconds And then subjected to post-baking at 230 캜 for 30 minutes in an oven. The pattern thus obtained was evaluated for physical properties as described below, and the results are shown in Table 2 below.

(1) Measurement of pattern vertical width ratio (T / B ratio)

Observing the obtained Dot pattern with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), a point 5% of the total height from the bottom surface of the pattern is referred to as Bottom CD (a) (= B / a x 100) obtained by dividing the length of (b) by the length of (a) and then multiplying by 100 is defined as a T / B ratio. Reference)

The pattern obtained was measured with a scanning electron microscope (Hitachi, S-4700), and the pattern shapes obtained between the compositions were compared.

2 (a) to 2 (e) are SEM photographs of the photocurable patterns formed by the compositions of Examples 1 to 5, and FIGS. 3 (a) to 3 SEM photograph of the photocuring pattern.

(2) Pattern of CD-bias

The pattern size obtained at the above-obtained film thickness of 3.0 占 퐉 is measured using a three-dimensional shape measuring apparatus (SIS-2000 system; manufactured by SNU Precision), and the difference from the mask size is calculated by CD-bias as follows. CD-bias is better the closer to 0, (+) means that the pattern is larger in size than the mask and (-) is smaller in size than the mask.

CD-bias = (formed pattern size) - (mask size used for forming)

(3) Measurement of adhesion

The development adhesion is determined by observing the degree of adhesion of the pattern generated by using a mask using a half-tone mask having a 25% transmittance to the substrate, and it is preferable that the size is 5 [micro] m to 20 [micro] m The actual size of the pattern when 100% of the pattern formed by the photomask having 1000 dots at intervals of 1 占 퐉 apart and having the film thickness of 3 占 퐉 remained without any missing was used by SIS-2000 of SNU Precision And the line width was measured. The value of the pattern line width was defined as the value of Bottom CD at 5% of the total height from the bottom surface of the pattern. The smaller the minimum pattern size remaining without loss, the more excellent the developing adhesion.

(4) the phenomenon Residual film ratio  evaluation

The resin compositions of Examples and Comparative Examples were applied to a substrate, spin-coated, and pre-baked at 90 DEG C for 125 seconds using a hot plate. After the prebaked substrate was cooled to room temperature. Light was irradiated onto the entire surface of the coating film with an exposure amount (based on 365 nm) of 60 mJ / cm 2 using an exposure machine (UX-1100SM; Ushio Co., Ltd.).

After light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 60 seconds and developed. After washing with water, post-baking was performed in an oven at 230 캜 for 30 minutes.

At this time, the film thickness after the exposure and the film thickness after the post-baking process were measured, and the residual film ratio was measured using the following equation.

The higher the residual film ratio, the better the performance.

division Example Comparative Example One 2 3 4 5 One 2 3 Bottom size (mm) 9.8 9.7 9.5 9.8 11.0 11.2 12.3 13.1 Top size (mm) 7.5 7.5 7.7 7.2 7.9 5.8 7.0 7.8 CD-Bias (mm) -0.2 -0.3 -0.5 -0.2 +1.0 1.2 2.3 3.1 T / B ratio 76% 77% 81% 74% 72% 52% 57% 59% Developability 12mm 11mm 11mm 12mm 13mm 17mm 15mm 14mm Residual film ratio 79% 82% 85% 81% 77% 65% 69% 71%

Referring to Table 2, it was confirmed that CB-Bias can be controlled while realizing a pattern of a small size as a whole in the case of the embodiment using the photosensitive resin composition according to the present invention.

In addition, it was confirmed that the embodiments of the present invention have excellent T / B ratio of pattern, improved adhesion to a substrate, and good developing property.

However, in the comparative examples not using the photosensitive resin composition according to the present invention, it was confirmed that the size of the pattern as a whole was large and the variation of the CD-bias was large, which was unsuitable for high resolution implementation.

Claims (10)

Soluble resin (1) comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2) and a repeating unit containing a carboxylic acid group in a main chain:
[Chemical Formula 1]

(2)

(Wherein R ₁ is independently of each other a hydrogen atom or a methyl group and R ₂ is, independently of each other, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 2 to 6 carbon atoms, An aromatic hydrocarbon group having 6 to 14 carbon atoms, and n is an integer of 1 to 9).
The photosensitive resin composition according to claim 1, further comprising an alkali-soluble second resin comprising a repeating unit represented by the following formula (3) and a repeating unit containing a carboxylic acid group in the main chain:
(3)

(Wherein R ₃ and R ₄ are, independently of each other, a hydrogen atom or a methyl group).
The photosensitive resin composition according to claim 1, wherein the alkali-soluble first resin is contained in an amount of 15 to 60 parts by weight based on 100 parts by weight of the solid content of the composition.
The photosensitive resin composition according to claim 2, wherein the alkali-soluble second resin is contained in an amount of 15 to 50 parts by weight based on 100 parts by weight of the total solid content of the composition.
The photosensitive resin composition according to claim 2, wherein a mixing weight ratio of the alkali-soluble first resin and the alkali-soluble second resin is 1: 0.15 to 2.5.
The photosensitive resin composition according to claim 1, further comprising a photopolymerizable compound, a photopolymerization initiator, and a solvent.
The photosensitive resin composition according to claim 2, further comprising a photopolymerizable compound, a photopolymerization initiator, and a solvent.
A photocurable pattern produced from the photosensitive resin composition according to any one of claims 1 to 7.
The photocurable pattern according to claim 8, wherein the photocurable pattern is selected from the group consisting of an adhesive layer, an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern and a column spacer pattern.
An image display apparatus comprising the photocurable pattern of claim 9.

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